Protective coating on positive lithium-metal-oxide electrodes for lithium batteries

ABSTRACT

A positive electrode for a non-aqueous lithium cell or battery in which the positive electrode comprising a LiMn 2−x M x O 4  spinel structure in which M is one or more cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0≦x≦0.15, having one or more lithium spine oxide LiM′ 2 O 4  or lithiated spinel oxide Li 1+y M′ 2 O 4  compounds in which the M′ cations are selected from one or more of lithium, cobalt, titanium or manganese and in which 0&lt;y≦1.

RELATED APPLICATIONS

[0001] This application, pursuant to 37 C.F.R. § 1.78(c), claims priority based on provisional application serial No. 60/352,899 filed Jan. 29, 2002.

CONTRACTUAL ORIGIN OF THE INVENTION

[0002] The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy (DOE) and The University of Chicago representing Argonne National Laboratory.

FIELD OF THE INVENTION

[0003] This invention relates to positive lithium metal oxide electrodes for lithium cells and batteries, preferably rechargeable lithium-ion cells and batteries. More specifically, it relates to a lithium metal oxide electrode with a spinel-related structure with a surface coating of one or more other lithium-containing spinel oxides that are structurally compatible with, but compositionally different from the structure of the bulk lithium metal oxide electrode, to protect the bulk electrode from capacity loss effects, such as oxygen loss and manganese dissolution during the electrochemical cycling of lithium-ion cells.

BACKGROUND OF THE INVENTION

[0004] State-of-the-art lithium-ion cells have a lithiated carbon negative electrode, or anode, (Li_(x)C₆) and a lithium-cobalt-oxide positive electrode, or cathode, Li_(1−x)CoO₂. During charge and discharge of the cells lithium ions are transported between the two host structures of the anode and cathode with the simultaneous oxidation or reduction of the host electrodes, respectively. When graphite is used as the anode, the voltage of the cell is approximately 4 V. The cathode material LiCoO₂, which has a layered structure, is expensive and becomes unstable at low lithium content, i.e., when cells reach an overcharged state at x≧0.5. Alternative less expensive electrode materials that are isostructural with LiCoO₂, such as LiNi_(0.8)Co_(0.2)O₂ and LiNi_(0.5)Mn_(0.5)O₂ are being developed in the hope of replacing at least part of the cobalt component of the electrode. However, all these layered structures, when extensively delithiated are unstable, because of the high oxygen activity at the surface of the particles; therefore, the electrode particles tend to react with the organic solvents of the electrolyte or lose oxygen.

[0005] Spinel electrodes, such as those in the manganese-based system Li_(1+x)Mn_(2−x)O₄, are particularly attractive alternatives to LiCoO₂ because, not only are they relatively inexpensive, but they are thermally more stable than Li_(1−x)CoO₂ or Li_(1−x)Ni_(0.8)Co_(0.2)O₂ at low lithium loadings, and because they do not contribute to the impedance rise of electrochemically cycled lithium-ion cells to the same extent as Li_(1−x)CoO₂ or Li_(1−x)Ni_(0.8)Co_(0.2)O₂ electrodes.

[0006] The Li_(1−x)[Mn₂]O₄ spinel system has been investigated extensively in the past as an electrode for lithium-ion batteries. A major reason why the spinel system has not yet been fully commercialized is because the electrode is unstable in the cell environment, particularly if the operating temperature of the cells is raised above room temperature, for example, to 40-60° C. It is now generally acknowledged that the solubility of Li_(x)[Mn₂]O₄ electrodes in acid medium occurs by the disproportionation reaction

Mn³⁺ _((solid))→Mn⁴⁺ _((solid))+Mn²⁺ _((solution))  (1)

[0007] during which the Mn²+ ions go into solution, and the Mn⁴+ ions remain in the solid spinel phase. Such a reaction can occur in lithium-ion cells because the hydrolysis of fluorinated lithium salts such as LiPF₆ with small amounts of residual water in the organic-based electrolyte solvents can generate hydrofluoric acid, HF.

[0008] Full electrochemical delithiation of Li[Mn₂]O₄ leaves λ-MnO₂ with the [Mn₂]O₄ spinel framework. Like many manganese dioxides, λ-MnO₂ is a powerful oxidizing agent and can be readily reduced. Therefore, any oxygen that may be evolved at the particle surface of the spinel electrode at the top of charge will result in Mn³+ ions at the electrode surface; the instability of Mn³+ ions at the high potential of the charged cell will also drive the disproportionation reaction (1) shown above, thus damaging the spinel surface and resulting in some irreversible capacity loss of the cell.

[0009] The presence of tetragonal Li₂[Mn₂]0 ₄ has also been observed in very small amounts at the surface of Li[Mn₂]O₄ spinel electrodes at the end of discharge after high rate cycling (C/3 rate) between 4.2 and 3.3 V vs. Li. The compound Li₂[Mn₂]O₄ in which all the manganese ions are trivalent will be unstable, like Li[Mn₂]O₄, at high potentials in a 1 M LiPF₆/EC/DMC electrolyte that contains HF, particularly if the lithium cells are operated at 40-50° C. In this case, a disproportionation reaction occurs in which MnO dissolves from the particle surface to leave an insoluble and stable Li₂MnO₃ rock-salt phase. This reaction may account for some of the capacity loss of 4-V Li/Li_(x)[Mn₂]O₄ cells on long-term cycling.

[0010] Substantial efforts have already been made in the past to overcome the solubility problems associated with the Li[Mn₂]O₄ spinel electrode. For example, partial substitution of the manganese ions in Li[Mn₂]O₄ with a mono-, di- or trivalent ion changes the composition of the electrode and increases the average oxidation state of the manganese ions above 3.5, thus reducing the amount of Mn³⁺ ions in the fully discharged electrode. Other approaches to suppress manganese dissolution from the spinel electrode have been taken, for example, by protecting the spinel particles with a surface coating, such as a low-melting lithium borate glass or a coating of LiCoO₂ applied at high temperature (e.g., 700-800° C.) both of which are known to be more resistant to dissolution in the electrolytes than Li[Mn₂]O₄. Alternatively, a coating of ZrO₂ or Co₃O₄ has been applied to the electrode particles. Although some success has been achieved by using these approaches, the problems of electrode instability have not yet been fully resolved and further improvements are necessary.

[0011] LiMn₂O₄ spinel electrodes have a tendency to lose oxygen or react with the electrolyte if charged to a high potential, such as 4.5 V, which causes irreversible capacity loss effects. Moreover, the loss of oxygen from the electrode can also contribute to exothermic reactions with the electrolyte and with the lithiated carbon negative electrode, and subsequently to thermal runaway if the temperature of the cell reaches a critical value. There is therefore a strong requirement to improve the state-of-the-art protective coatings on these electrodes to improve the overall performance and safety of lithium-ion cells.

SUMMARY OF THE INVENTION

[0012] This invention relates to an improved LiMn_(2−x)M_(x)O₄ positive electrode (0≦x≦0.15) with a spinel-related structure for non-aqueous lithium cells and batteries, preferably rechargeable lithium-ion cells and batteries. More specifically, it relates to a LiMn_(2−x)M_(x)O₄ spinel electrode with a surface coating of one or more other lithium spinel oxides LiM′₂O₄ or lithiated LiM′₂O₄ spinel oxides Li_(1+y)M′₂O₄ (0<y≦1) that are structurally compatible with, but compositionally different from the structure of the bulk LiMn_(2−x)M_(x)O₄ spinel electrode, to protect the spinel electrode in the bulk from capacity loss effects, such as oxygen loss and/or manganese dissolution during the electrochemical cycling of lithium-ion cells. The bulk LiMn_(2−x)M_(x)O₄ spinel electrode is comprised of the family of cation-stabilized spinels LiMn_(2−x)M_(x)O₄, in which M is one or more of any mono or multivalent cations with an atomic number less than 52, preferably with an atomic number less than 33, such as monovalent Li⁺or H⁺, divalent Mg²⁺or Co²⁺, trivalent Al³⁺or Co³⁺, tetravalent Ti⁴⁺or Zr⁴⁺, or the like, such that the average oxidation state of the manganese ions is equal to or greater than 3.5. The lithium spinel oxide or lithiated spinel oxide coatings are comprised of LiM′₂O₄ or Li_(1+y)M′₂O₄ compounds in which the M′ cations are selected from one or more of lithium, cobalt, titanium or manganese, preferably lithium and/or cobalt, for example, a lithium-cobalt-oxide spinel Li_(x)Co_(3−x)O₄ (0<x<0.4), or alternatively, the low-temperature, lithiated-spinel form of LiCoO₂ (i.e., Li₂Co₂O₄) in which the CoO₂ component has a [Co₂]O₄ spinel-like framework. Other examples include the lithium spinel oxides Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄, or their electronically-conducting Li—, Mg— or Al—substituted derivatives to induce mixed valence character to the Ti and Mn transition metal cations and hence electronic conductivity to the spinel coating.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The invention consists of certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, and particularly pointed out in the appended claims, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.

[0014]FIG. 1 depicts the powder X-ray diffraction pattern of a Li_(1.03)Mn_(1.97)O₄ electrode coated with a lithium-cobalt-oxide spinel, the coating prepared by a sol-gel method from lithium acetate and cobalt acetate precursors at 400° C.;

[0015]FIG. 2 depicts a transmission electron micrograph of the surface of a Li_(1.03)Mn_(1.97)O₄ electrode coated with a lithium-cobalt-oxide spinel, the X-ray diffraction pattern of which is shown in FIG. 1;

[0016]FIG. 3 depicts the powder X-ray diffraction pattern of a Li_(1.03)Mn_(1.97)O₄ electrode coated with a lithium-cobalt-oxide spinel, the coating prepared from octacarbonyidicobalt with 1-5 mole percent hexane stabilizer and lithium carbonate precursors at 400° C.;

[0017]FIG. 4 depicts the electrochemical profile of a standard Li/Li_(1.03)Mn_(1.97)O₄ cell and a Li/Li_(1.03)Mn_(1.97)O₄ cell in which the Li_(1.03)Mn_(1.97)O₄ electrode was coated with LiCoO₂ by a sol-gel method at 400° C.;

[0018]FIG. 5(a)-(c) depict plots of electrode capacity vs. cycle number of a) a standard Li/Li_(1.03)Mn_(1.97)O₄ cell and b) and c) Li/Li_(1.03)Mn_(1.97)O₄ cells in which the Li_(1.03)Mn_(1.97)O₄ electrode was coated with a lithium-cobalt-oxide spinel;

[0019]FIG. 6 depicts a schematic illustration of an electrochemical cell; and

[0020]FIG. 7 depicts a schematic illustration of an example of a battery employing the cells of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0021] This invention relates to an improved LiMn_(2−x)M_(x)O₄ spinel electrode (0≦x≦0.15), in which M is one or more of any mono or multivalent cations with an atomic number less than 52, preferably with an atomic number less than 33, such as monovalent Li⁺or H⁺, divalent Mg²⁺ or Co²⁺, trivalent Al³⁺or Co³⁺, tetravalent Ti^(4+ or Zr) ⁴⁺, or the like, such that the average oxidation state of the manganese ions is equal to, or greater than 3.5 for lithium cells and batteries, preferably rechargeable lithium-ion cells and batteries. More specifically, it relates to a LiMn_(2−x)M_(x)O₄ spinel electrode with a surface coating of one or more other lithium spinel oxides LiM′₂O₄ or lithiated LiM′₂O₄ spinel oxides Li_(1+y)M′₂O₄ (0<y≦1) that are structurally compatible with, but compositionally different to the structure of the bulk LiMn_(2−x)M_(x)O₄ spinel electrode, to protect the bulk spinel electrode from capacity loss effects, such as oxygen loss and/or manganese dissolution during the electrochemical cycling of lithium-ion cells.

[0022] Of particular significance to this invention is the realization that in order to achieve good binding between a surface protective coating consisting of one or more lithium-metal oxides with the lithium metal oxide structure of the bulk electrode, it is important to have a strong structural compatibility between the surface coating and the structure of the bulk electrode. Therefore, according to the invention, both the lithium metal oxide of the surface coating and the bulk electrode have spinel structures which are close-packed, preferably cubic-close-packed or approximately cubic-close-packed, with compatible crystallographic parameters that allow the structure of the coating to be fused to, or intergrown with, or connected to the structure of the bulk of the particle at the coating/bulk interface.

[0023] Attempts have been made in the past to coat Li[Mn₂]O₄ spinel particles with LiCoO₂ at high temperature, typically 800° C. At this temperature, LiCoO₂ has a layered structure with trigonal symmetry (R-3m, a=2.82 Å, c=14.06 Å), whereas Li[Mn₂]O₄ has a spinel structure with cubic symmetry (Fd-3m, a=8.24 Å). There is thus an incompatibility in structure types between the LiCoO₂ coating and the spinel structure of the bulk electrode, which may affect 1) the integrity of the surface layer, particularly at the surface/bulk interface during cycling and 2) its adhesion to the spinel particles. Stabilizing Li[Mn₂]O₄ spinel electrodes can be achieved with other spinel compounds with cubic Fd-3m symmetry or close to cubic symmetry, with lattice parameters close to that of the Li[Mn₂]O₄ spinel electrode. In this respect, there are a number of suitable candidate materials with a spinel structure are useful as a protective coating. One such compound is the lithiated spinel Li₂[Co₂]O₄ which, although having the same formula as layered LiCoO₂, has a different structure; Li₂[Co₂]O₄ can be synthesized at a lower temperature than layered LiCoO₂, typically at 400° C. or lower. For example, the lattice parameter of a Li_(1−x)[Mn₂]O₄ electrode changes from 8.24 to 8.03 A for the range 0<x<1. The lithiated spinel Li₂[Co₂]O₄ has a lattice parameter of approximately the same dimension (8.00 Å), and this parameter does not change significantly on lithium extraction to the stoichiometric spinel composition Li[Co₂]O₄. Thus, according to the invention, the cobalt spinel has suitable structural characteristics for the protective layer. Furthermore, it is known that LiCoO₂ materials can be fabricated at moderate temperatures (e.g., between 400 and 500° C. with a cation distribution which is intermediate between that of layered-LiCoO₂ and lithiated-spinel LiCoO₂ (Li₂[Co₂]O₄). The applicants believe that such intergrown materials with spinel-related character provide greater stability than the structures with the ideal spinel arrangement of cations. The invention also includes lithium-substituted cobalt oxide spinels Li_(x)Co_(3−x)O₄ that have been reported to exist over the range 0<x<0.4 by N. K. Appandairajan et al in the Journal of Power Sources, Volume 40, pages 117-121 (1981), as the protective coating. The protective layers or coatings need not be uniform or homogeneous; indeed it has been found that the layers or coatings can be comprised of individual or interconnected grains that are fused to the surface of the bulk spinel particles. Therefore in a preferred embodiment, the invention includes lithium spinel oxides LiM′0 ₄ or lithiated LiM₂O₄ spinel oxides Li_(1+y)M′₂O₄ (0<y<1) in which M′ can be selected from lithium and/or cobalt on the surface of the LiMn_(2−x) M_(x)O₄ electrode.

[0024] It is known in the art of lithium battery technology that LiMn₂O₄ spinel electrodes can be stabilized by substituting Co²⁺or Co³⁺ions for the Mn^(4+/3+) ions in the bulk of the spinel structure, thereby reducing the concentration of Mn³⁺ ions in the spinel framework and increasing the stability of the spinel electrode. Such Co-stabilized spinels can be represented as Li[Mn_(2−x)Co_(x)]O₄ in which x can be typically 0.15 or less, preferably 0.05 or less. Therefore, in a yet a further embodiment of this invention, these stabilized spinels can be used to good effect by introducing a concentration gradient of cobalt in the spinel framework, which increases from a low concentration at the center of the electrode particle (e.g., with composition [Mn_(1.85)Co_(0.15)]O₄) to a high concentration at the surface (e.g., [Co₂]O₄). The gradual change in lattice parameter of the spinel electrode associated with change in Co concentration, it is believed will contribute to the structural stability of the electrode and to enhanced stability at the electrode surface.

[0025] The principles of this invention as described above can be extended to include other lithium spinel materials or lithiated spinels as the protective layer, for example, LiM′₂O₄ or Li_(1+y)M′₂O₄ spinel-related compounds in which M′ is selected from one or more cations of lithium, titanium and manganese, such as the lithium spinel oxides Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄, that have lattice parameters of a=8.36 Å and a=8.14 Å, respectively, close to the typical lattice parameters of the LiMn_(2−x)M_(x)O₄ bulk spinel electrodes of this invention (≦8.24 Å). It has already been well documented in the literature that many spinel oxides with a wide variety of compositions can be synthesized in the laboratory, such as those having cations with an atomic number less than 52 as reported by R. J. Hill et al in Phys. Chem. Minerals, Volume 4, pages 317 to 339 (1979). It is also well known in the art that lithium ions can be ion-exchanged with protons (H⁺ions) from typical electrolytes of lithium cells, thereby leading to the incorporation of the H⁺ ions within the spinel electrode structure on storage and during the electrochemical operation of cells. In a particular embodiment, the invention includes Li—, Mg— or Al—substituted derivatives of the lithium spinel oxides LiM′₂O₄ or Li_(1+y)M′₂O₄ such as Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄ as reported by C. H. Chen et al in the Journal of the Electrochemical Society, Volume 148(1), pages A102 to A103 (2001) to induce mixed valence character to the Ti and Mn transition metal cations and hence electronic conductivity to the spinel coating, examples for the lithium titanate spinel coating being Li[Ti_(1.67+z)Li_(0.33−z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Mg_(z)]O₄ and Li[Ti_(1.67)Li_(0.33)Al_(z)]O₄ for the lithium manganate spinel coating being Li[Mn_(1.67)Li_(0.33−z)Mg_(z)]O₄ and Li[Mn_(1.67)Li_(0.33−z)Al_(z)]O₄ for 0<z<0.2. A particular advantage of using LiMn_(2−x)M_(x)O₄, LiM′₂O₄ or Li_(1+y)M′₂O₄ lithium spinel oxides that contain some aluminum ions, titanium ions or zirconium ions is that these ions bond strongly to the oxygen framework of the spinel, thus providing additional structural stability to the electrode. The following examples describe possible methods of synthesizing the coated lithium-metal oxide electrodes of this invention as contemplated by the inventors, but they are not to be construed as limiting examples.

EXAMPLE 1

[0026] A sample of Li_(1.03)Mn_(1.97)O₄ spinel powder was suspended in methanol, to which was added a 1:1 molar ratio of lithium acetate and cobalt acetate, such that the LiCoO₂ content in the final electrode was 3 percent by weight. The mixture was thoroughly stirred. The methanol was removed by rotary evaporation. The resulting product was heat treated under flowing oxygen at 400° C. for 96 hours. The X-ray diffraction pattern of the lithium-cobalt-oxide-coated Li_(1.03)Mn_(1.97)O₄ sample is compared with the parent, uncoated Li_(1.03)Mn_(1.97)O₄ starting material, as shown in FIG. 1. FIG. 1 demonstrates that the X-ray diffraction pattern of the coated sample is effectively identical to that of the parent uncoated spinel material. A transmission electron microscope image of the Li—Co—O spinel coating on a Li—Mn—O spinel particle is shown in FIG. 2. An EDAX (Electron Dispersion Analysis of X-rays) analysis of the coating showed unequivocally that the surface coating contained cobalt and that the bulk of the electrode particle contained manganese. However, the applicants believe that diffusion of lithium, cobalt and manganese takes place within the close-packed oxygen array and at the phase boundaries during the coating process at 400° C. Therefore, concentration gradients at the coating/bulk interface of the electrodes. FIG. 2 clearly shows in broad outline the distinguishing boundary that connects the Li—Co—O spinel coating and the Li—Mn—O spinel in the bulk of the particle. FIG. 2 also demonstrates that the coating, when applied by the sol-gel technique, is not homogeneous or uniform, and that it is comprised of individual, but interconnected grains of Li—Co—O spinel that contain planar defects, the directions of which are indicated by the dotted arrows in FIG. 2.

EXAMPLE 2

[0027] A sample of Li_(1.03)Mn_(1.97)O₄ spinel powder was suspended in hexane with rapid stirring. A predetermined quantity of octacarbonyldicobalt with 1-5 mole percent hexane as stabilizer, designated Co₂(CO)₈C₆H₁₄, and Li₂CO₃ (Li:Co ratio=1:1) was used to fabricate a lithium-cobalt-oxide spinel coating such that the overall composition of the spinel electrode was 0.2LiCoO₂0.8Li_(1.03)Mn_(1.97)O₄. The Co₂(CO)₈C₆H₁₄ was dissolved in hexane and added to the LiMn₂O₄ sample together with the required quantity of Li₂CO₃. The temperature was raised slowly to evaporate the hexane. The resulting product was then heat treated under flowing oxygen at 400° C. for 96 hrs. The X-ray diffraction pattern of the coated Li_(1.03)Mn_(1.97)O₄ sample is shown in FIG. 3. This X-ray diffraction pattern provides evidence of the coated Li_(1.03)Mn_(1.97)O₄ sample as well as a detectable amount of a spinel-related Li_(x)Co_(3−x)O₄ product, as evident from the weak [220] peak at approximately 31.5° 2θ and peak shoulders (arrowed) that are located to the right of the coated Li_(1.03)Mn_(1.97)O₄ peaks. The detection of a Li_(x)Co_(3−x)O₄ product in the electrode sample is attributed to the relatively high concentration of cobalt precursor used in Example 2 compared with Example 1.

EXAMPLE 3

[0028] Standard spinel electrodes of approximate composition Li_(1.03)Mn_(1.97)O₄, and those that had been coated with lithium cobalt oxides with spinel-related structures at a moderate temperature (400° C.), were evaluated in coin cells (size 2032, with dimensions 20 mm diameter and 3.2 mm high) against a counter lithium electrode. The cells had the configuration: Li/1M LiPF₆ in ethylene carbonate (EC), diethyl carbonate (DEC) (1:1)/Li_(1.03)Mn_(1.97)O₄. Electrodes were fabricated with approximately 7 to 10 mg of the spinel powder, i.e., approximately 82% by weight of the laminate electrode, intimately mixed with approximately 10% by weight of a polyvinylidene difluoride binder (Kynar or Kureha-type PVDF polymer) and approximately 8% by weight of carbon (graphite, such as Timcal SFG-6, or acetylene black, such as Chevron XC-72) in 1-methyl-2-pyrrolidinone (NMP). The slurries were coated with a doctor blade onto an aluminum foil substrate current collector. The electrode laminates were dried under vacuum at temperatures from 40 to 110° C.; electrodes of suitable size were punched from these laminates to fit the coin cells. Metallic lithium foil was used as the counter electrode. The coin cells were discharged and charged at constant current (typically 0.1 mA/cm²) within the voltage range 4.3 to 3.3 V.

[0029] The electrochemical voltage profiles, obtained on the fifth cycle between 4.3 and 3.3 V at 50° C., of a standard Li/Li_(1.03)Mn_(1.97)O₄ cell and a Li/Li_(1.03)Mn_(1.97)O₄ cell in which the spinel electrode had been coated by the sol-gel method described in Example 1 are provided in FIG. 4. The voltage profile of the cell with a coated spinel electrode shows a short plateau at approximately 3.6 V, which is absent in the profile of the standard Li/Li_(1.03)Mn_(1.97)O₄ cell; this feature is consistent with the electrochemical behavior of LiCoO₂ with a spinel-related structure Li₂[Co₂]O₄, synthesized at 400° C.

[0030]FIG. 5 shows plots of electrode discharge capacity versus cycle number for lithium cells that contained the standard, uncoated Li_(1.03)Mn_(1.97)O₄ electrode and the coated electrodes of Examples 1 and 2. The data in FIG. 5 indicate that at 50° C. the rate of capacity fade of the coated electrodes is significantly less than that of the standard electrode, thereby demonstrating the effectiveness of the coating. The theoretical capacity of the coated spinel electrode of Example 1, taking into account the capacity of the electrochemically active LiCoO₂ coating, is 140 mAh/g. After 25 cycles at 50° C., this coated electrode delivers a discharge capacity of approximately 111 mAh/g (i.e., 79% of its theoretical capacity), in contrast to 103 mAh/g delivered by the standard spinel electrodes, which is 76% of its theoretical capacity (136 mAh/g). Of major significance, however, is that the rate of capacity fade of the coated electrode for the first 25 cycles is 0.14% per cycle, whereas for the standard electrodes it is 0.50% per cycle.

[0031] Although FIG. 5 shows that the capacity of the coated electrode of Example 2 is less than that of the standard, uncoated Li_(1.03)Mn_(1.97)O₄ electrode, the inferior capacity of the coated electrode is attributed to the relatively high cobalt content used for the coating that resulted in an appreciable amount of spinel-related Li_(x)Co_(3−x)O₄ in the electrode which does not contribute significantly to the capacity of the cells when charged and discharged between 4.3 and 3.3 V. Nevertheless, the rate of capacity fade of the coated electrode of Example 2 is significantly superior to that of the standard, uncoated Li_(1.03)Mn_(1.97)O₄ electrode. Moreover, the rate of capacity fade of the coated electrode of Example 2 is essentially the same as the rate of capacity fade of the coated electrode of Example 1 as reflected by the closely parallel slopes of their capacity vs. cycle number plots in FIG. 5. Therefore, the inventors believe that the practical capacity of coated electrodes made in accordance with the method of Example 2 will be increased by reducing the amount of Co₂(CO)₈C₆H₁₄ and Li₂CO₃ precursors used for making the Li—Co—O coating.

[0032] The examples and data provided above demonstrate the principles of this invention. In particular, they show that improved electrochemical performance of a non-aqueous lithium cell can be achieved by coating a LiMn₂O₄ spinel positive electrode with a lithium-containing spinel compounds that are structurally compatible with, but compositionally different from the structure of the bulk LiMn₂O₄ spinel electrode, to provide a good lattice match between the bulk electrode structure and the structure of the electrode coating, and to protect the spinel electrode in the bulk from capacity loss effects, such as oxygen loss and/or manganese dissolution during the electrochemical cycling of lithium-ion cells.

[0033] This invention, therefore, relates to positive electrodes for a non-aqueous electrochemical lithium cell, as shown schematically in FIG. 13, the cell represented by the numeral 10 having a negative electrode 12 separated from a positive electrode 16 by an electrolyte 14, all contained in an insulating housing 18 with suitable terminals (not shown) being provided in electronic contact with the negative electrode 12 and the positive electrode 16. Binders and other materials normally associated with both the electrolyte and the negative and positive electrodes are well known in the art and are not described herein, but are included as is understood by those of ordinary skill in this art. FIG. 14 shows a schematic illustration of one example of a battery in which two strings of electrochemical lithium cells, described above, are arranged in parallel, each string comprising three cells arranged in series.

[0034] While there has been disclosed what is considered to be the preferred embodiments of the present invention, it is understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention and that additional improvements in the capacity and stability of the electrodes can be expected to be made in the future by improving and optimizing the processing techniques whereby electrodes are coated with protective layers. 

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
 1. A positive electrode for a non-aqueous lithium cell comprising a LiMn_(2−x)M_(x)O₄ spinel structure in which M is one or more cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0≦x≦0.15, having one or more lithium spinel oxide LiM′₂O₄ or lithiated spinel oxide Li_(1+y)M₂O₄ compounds on the surface thereof in which the M′ cations are selected from one or more of lithium, cobalt, titanium or manganese and in which 0<y≦1.
 2. An electrode according to claim 1 in which in which M is one or more cations with an atomic number less than
 33. 3. An electrode according to claim 1 in which M is selected from one or more of H⁺, Li⁺, Mg²⁺, Co²⁺, Al³⁺, Co³⁺, Ti⁴⁺ and Zr⁴⁺ cations.
 4. An electrode according to claim 1 in which the M and M′ cations are selected from lithium and/or cobalt.
 5. An electrode according to claim 4 in which the LiM′₂O₄ coating is Li_(x)Co_(3−x)O₄ for 0<x<0.4.
 6. An electrode according to claim 4 in which the Li_(1+y)M′₂O₄ coating is Li₂Co₂O₄.
 7. An electrode according to claim 1 in which the M′ cations are selected from lithium, titanium, manganese or mixtures thereof.
 8. An electrode according to claim 7 in which the LiM′₂O₄ coating is Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 9. An electrode according to claim 8 in which the LiM′₂O₄ coating is a Li—, Mg— or Al—substituted derivative of Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 10. An electrode according to claim 9 in which the LiM′₂O₄ coating is Li[Ti_(1.67+z)Li_(0.33−z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Mg_(z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Al_(z)]O₄, Li[Mn_(1.67)Li_(0.33−z)Mg_(z)]O₄ or Li[Mn_(1.67)Li_(0.33−z)Al_(z)]O₄ for 0<z<0.2.
 11. The positive electrode of claim 1, wherein spinel oxide is present as a coating.
 12. The positive electrode of claim 1, wherein the concentration of M′ cations increases from the center to the surface of the electrode.
 13. A non-aqueous lithium electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode, the positive electrode comprising a LiMn_(2−x)M_(x)O₄ spinel structure in which M is one or more cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0<x<0.15, having one or more lithium spinel oxide LiM′₂O₄ or lithiated spinel oxide Li_(1+y)M′₂O4 compounds in which the M′ cations are selected from one or more of lithium, cobalt, titanium or manganese and in which 0<y≦1.
 14. A non-aqueous lithium electrochemical cell of claim 13, in which M is selected from one or more of H⁺, Li⁺, Mg²⁺, Co²⁺, Al³⁺, Co³⁺, Ti⁴⁺ or Zr⁴⁺ cations.
 15. A non-aqueous lithium electrochemical cell of claim 13, in which the M and M′ cations are selected from lithium, cobalt and mixtures thereof.
 16. A non-aqueous lithium electrochemical cell of claim 15, in which the LiM′₂O₄ coating is Li_(x)Co_(3−x)O₄ for 0<x<0.4.
 17. A non-aqueous lithium electrochemical cell of claim 15, in which the Li_(1+y)M′₂O₄ coating is Li₂Co₂O₄.
 18. A non-aqueous lithium electrochemical cell of claim 13, in which the M′ cations are selected from lithium, titanium, manganese or mixtures thereof.
 19. A non-aqueous lithium electrochemical cell of claim 18, in which the LiM′₂O₄ coating is Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 20. A non-aqueous lithium electrochemical cell of claim 19, in which the LiM′₂O₄ coating is a Li—, Mg— or Al—substituted derivative of Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 21. A non-aqueous lithium electrochemical cell of claim 18, in which the LiM′₂O₄ coating is Li[Ti_(1.67+z)Li_(0.33−z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Mg_(z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Al_(z)]O₄, Li[Mn_(1.67)Li_(0.33−z)Mg_(z)]O₄ or Li[Mn_(1.67)Li_(0.33−z)Al_(z)]O₄ for 0<z<0.2.
 22. The positive electrode of claim 13, wherein spinel oxide is present as a coating.
 23. The positive electrode of claim 13, wherein the concentration of M′cations increases from the center to the surface of the electrode
 24. A non-aqueous lithium battery comprising a plurality of electrochemical cells, electrically connected, each cell comprising a negative electrode, an electrolyte and a positive electrode, the positive electrode comprising a LiMn_(2−x)M_(x)O₄ spinel structure in which M is one or more cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0<x<0.15, having one or more lithium spinel oxide LiM′₂O₄ or lithiated spinel oxide Li_(1+y)M′₂O₄ compounds in which the M′ cations are selected from one or more of lithium, cobalt, titanium or manganese and in which 0<y≦1.
 25. A non-aqueous lithium battery of claim 24, in which M is selected from one or more of H⁺, Li⁺, Mg²⁺, Co²⁺, Al³⁺, Co³⁺, Ti⁴⁺ or Zr⁴⁺ cations.
 26. A non-aqueous lithium battery of claim 24, in which the M and M′cations are selected from lithium, cobalt or mixtures thereof.
 27. A non-aqueous lithium battery of claim 26, in which the LiM′₂O₄ coating is Li_(x)Co_(3−x)O₄ for 0<x<0.4.
 28. A non-aqueous lithium battery of claim 26, in which the Li_(1+y)M′₂O₄ coating is Li₂Co₂O₄.
 29. A non-aqueous lithium battery of claim 24, in which the M′ cations are selected from lithium, titanium, manganese or mixtures thereof.
 30. A non-aqueous lithium battery of claim 29, in which the LiM′₂O₄ coating is Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 31. A non-aqueous lithium battery of claim 30, in which the LiM′₂O₄ coating is a Li—, Mg— or Al—substituted derivative of Li[Ti_(1.67)Li_(0.33)]O₄ or Li[Mn_(1.67)Li_(0.33)]O₄.
 32. A non-aqueous lithium battery of claim 31, in which the LiM′₂O₄ coating is Li[Ti_(1.67+z)Li_(0.33−z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Mg_(z)]O₄, Li[Ti_(1.67)Li_(0.33−z)Al_(z)]O₄, Li[Mn_(1.67)Li_(0.33−z)Mg]O₄ or Li[Mn_(1.67)Li_(0.33−z)Al_(z)]O₄ for 0<z<0.2.
 33. The positive electrode of claim 24, wherein spinel oxide is present as a coating.
 34. The positive electrode of claim 24, wherein the concentration of M′ cations increases from the center to the surface of the electrode 